16883-74-2Relevant academic research and scientific papers
Manganese(iii) acetate-mediated direct C(sp2)-H-sulfonylation of enamides with sodium and lithium sulfinates
Kramer, Philipp,Krieg, Sara-Cathrin,Kelm, Harald,Manolikakes, Georg
, p. 5538 - 5544 (2019)
A Mn(OAc)3 mediated oxidative C(sp2)-H sulfonylation of enamides and encarbamates with sodium and lithium sulfinates is reported. This operationally simple transformation provides a straightforward and highly stereoselective access to (E)-β-amidovinyl sulfones in moderate to excellent yields. The reaction proceeds readily under mild conditions at room temperature and tolerates various sensitive functional groups. This process affords exclusively (E)-configurated β-amidovinyl sulfones independent of the starting material configuration. Moreover, a direct transformation of organolithium reagents and sulfur dioxide into β-amidovinyl sulfones is described.
Copper-Mediated Sulfonylation of Aryl C(sp2)-H Bonds with Sodium and Lithium Sulfinates
Liang, Shuai,Liu, Nai-Wei,Manolikakes, Georg
, p. 159 - 163 (2016)
A copper-mediated direct sulfonylation of aryl C(sp2)-H bonds with sodium and lithium sulfinates is reported. Various aryl sulfones were synthesized in moderate to excellent yields with good functional group tolerance.
Nickel(II)-Catalyzed Synthesis of Sulfinates from Aryl and Heteroaryl Boronic Acids and the Sulfur Dioxide Surrogate DABSO
Lo, Pui Kin Tony,Chen, Yiding,Willis, Michael C.
, p. 10668 - 10673 (2019/11/11)
We report a redox-neutral Ni(II)-catalyzed sulfination of readily available aryl and heteroaryl boronic acids. Using the combination of commercially available, air-stable NiBr2·(glyme), a commercially available phenanthroline ligand, and DABSO, boronic acids are efficiently converted to the corresponding sulfinate salts, which can be further elaborated to valuable sulfonyl-containing groups, including sulfones, sulfonamides, sulfonyl fluorides, and sulfonate esters. The catalyst loading can be reduced to 2.5 mol ?% on a gram scale. This practically simple protocol tolerates an unprecedented range of pharmaceutically relevant and electron-poor (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients.
Copper-Catalyzed Remote para-C?H Functionalization of Anilines with Sodium and Lithium Sulfinates
Liang, Shuai,Bolte, Michael,Manolikakes, Georg
supporting information, p. 96 - 100 (2017/01/09)
A copper-catalyzed, cross-dehydrogenative coupling of anilines with sodium and lithium sulfinates was developed. By using a cooperative reaction system with Mn(OAc)3as stoichiometric co-oxidant a highly selective para-functionalization of anilines was accomplished. Various functional groups were tolerated and the desired products were obtained in high yields. This method not only provides a novel approach for the synthesis of arylsulfones but might also offer new opportunities for the development of copper-catalyzed para-selective C?H functionalizations.
Manganese(III) Acetate Mediated C–H Sulfonylation of 1,4-Dimethoxybenzenes with Sodium and Lithium Sulfinates
Liang, Shuai,Ren, Yueling,Manolikakes, Georg
supporting information, p. 4117 - 4120 (2017/08/07)
A simple and mild Mn(OAc)3-promoted oxidative coupling of 1,4-dimethoxybenzenes with sodium and lithium sulfinates was developed. The reaction proceeded readily at room temperature in air, and various sulfones were synthesized in moderate to high yields. In addition, a straightforward approach for the conversion of organolithium reagents and sulfur dioxide into sulfonylated 1,4-dimethoxybenzenes was explored.
Copper-Catalyzed Remote C?H Functionalization of 8-Aminoquinolines with Sodium and Lithium Sulfinates
Liang, Shuai,Manolikakes, Georg
supporting information, p. 2371 - 2378 (2016/08/16)
A simple and mild copper-catalyzed sulfonylation of 8-aminoquinolines with sodium and lithium sulfinates is reported. In the presence of manganese(III) acetate [Mn(OAc)3] as cooxidant a highly site-selective C?H functionalization at the C-5 position takes place. The reaction proceeds readily at room temperature in air and various sulfones were synthesized in moderate to high yields. Moreover, a straightforward procedure for the conversion of organolithium reagents and sulfur dioxide into C-5 sulfonylated quinolines was developed. (Figure presented.).
One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts
Margraf, Natalie,Manolikakes, Georg
, p. 2582 - 2600 (2015/03/18)
A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.
Arylation of lithium sulfinates with diaryliodonium salts: A direct and versatile access to arylsulfones
Umierski, Natalie,Manolikakes, Georg
supporting information, p. 4972 - 4975 (2013/10/22)
An efficient, transition-metal-free arylation of lithium sulfinates, which are readily accessible from reactions of organolithium reagents with sulfur dioxide, is described. Based on this method, a practical protocol for the direct transformation of (hetero)arenes and (hetero)aromatic halides into diarylsulfones was developed.
Synthesis and characterization of lithium oxonitrate (LiNO)
Switzer, Christopher H.,Miller, Thomas W.,Farmer, Patrick J.,Fukuto, Jon M.
, p. 128 - 133 (2013/02/23)
The oxonitrate(1 -) anion (NO-), the one-electron reduction product of nitric oxide and conjugate base of HNO, has not been synthesized and isolated due to the inherent reactivity of this anion. The large scale synthesis and characterization of a stable NO- salt is described here. The lithium salt of oxonitrate (LiNO) was formed by the deprotonation of N-hydroxybenzenesulfonamide with phenyllithium in aprotic, deoxygenated conditions. LiNO exhibited antiferromagnetic paramagnetism as determined by SQUID magnetometry, consistent with a triplet ground state of NO-. LiNO reacted with HCl to yield nitrous oxide consistent with HNO formation and dimerization. LiNO consumed O2 in a pH-dependent manner to initially produce peroxynitrite and eventually nitrite. Consistent with the reduction potential of NO, LiNO exhibited an oxidation potential of approximately + 0.80 V as determined by reactions with a series of viologen electron acceptors. LiNO also reacted with ferric tetraphenylporphyrin chloride (Fe(TPP)Cl), potassium tetracyanonickelate (K2Ni(CN)4) and nitrosobenzene in a manner that is identical to other HNO/NO- donors. We conclude that the physical and chemical characteristics of LiNO are indistinguishable from the experimentally and theoretically derived data on oxonitrate (1 -) anion. The bulk synthesis and isolation of a stable 3NO- salt described here allow the chemical and physical properties of this elusive nitrogen oxide to be thoroughly studied as this once elusive nitrogen oxide is now attainable.
Oxidation of aromatic lithium thiolates into sulfinate salts: An attractive entry to aryl sulfones labeled with carbon-11
Martin, Claudie,Sandrinelli, Franck,Perrio, Cecile,Perrio, Stephane,Lasne, Marie-Claire
, p. 210 - 214 (2007/10/03)
Aromatic 11C-sulfones were synthesized by S alkylation of lithium arenesulfinates, which are readily available from the corresponding thiols by an oxaziridine-mediated oxidation reaction with [11C]alkyl iodides in THF/H2O (4:1) at 150 °C. The radiosyntheses, including purification by HPLC, were completed in an average of 35 min from the end of the bombardment with 55-76% overall radiochemical yields (decay corrected). The described procedure extends the range of accessible labeling methods.
